Sublimable insecticidal compositions containing triisopropyl- or tritertiary-butyl-s-trioxane carriers

ABSTRACT

An improvement is provided in sublimable agricultural chemical compositions in the form of rough grains, pulverized powders or tablets which comprises at least one agricultural chemical and a carrier therefor. The improvement resides in the employment as the carrier, triisopropyl-s-trioxane or tritertiary-butyl-s-trioxane.

CROSS REFERENCE TO RELATED APPLICATION

This is a continuation-in-part of Ser. No. 463,176, filed Apr. 22, 1974,now abandoned.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to sublimable agricultural chemicalcompositions in the form of rough granules, pulverized powders ortablets comprising triisopropyl-s-trioxane (hereinafter referred to astrioxane (1)) or tritertiarybutyl-s-trioxane (hereinafter referred to astrioxane (2)) as a diluent or carrier and one or more agriculturalchemicals mixed therewith. In the above, the term agricultural chemicalsmeans insecticides, fungicides, rodenticides, herbicides, supplementalagents and the like, and the term sublimable agricultural compositionsincludes a broader range of materials such as insecticides forenvironmental sanitation, especially for domestic use.

2. Description of the Prior Art

Conventionally, agricultural chemical compositions including fungicides,insecticides, rodenticides, herbicibes, supplemental agents or the likehave been used in the form of wettable powders, emulsions, powders,granules, aerosols and the like. Among them, those in the form of powderand grain each comprise a carier or a diluent in a powdery state such assulfur, silicon, talc, diatomaceous earth, silica, calcium hydroxide,apatite, calcite, dolomite, gypsum, mica, pyrophyllite, clay, pumice andthe like and one of the agricultural chemicals mixed therein.

SUMMARY OF THE INVENTION

A main object of the present invention is to provide diluents orcarriers superior in properties to conventional ones as above-mentioned.

Most of conventional diluents or carriers used in solid agriculturalcompositions were inorganic substances or compounds and agriculturalchemicals merely attached to their surface or were mixed therewith. Suchconventional carriers were also unable to prevent the decomposition ofagricultural chemicals and remained in the soil after use withoutsubliming.

In contrast, when either mixed directly with an agricultural chemical ormixed therewith after melting, the two trioxanes of the presentinvention produce agricultural chemical compositions in which theagricultural chemical is contained in a crystalline trioxane. Therefore,the chemical hardly decomposes or changes in nature. When thecomposition is used on the soil, both of the trioxanes of the presentinvention gradually sublime with the result that the chemicals remaineffective for a long period of time. Neither trioxane in the soil. Thesublimable agricultural chemical compositions of the present inventionmay be sprinkled in the air, on the soil, or in a paddy field.

Trioxane (1) or (2) used as a diluent or carrier for manufacturing thesublimable agricultural chemical compositions in the present inventionare characterized by the following advantages over conventional carriersor diluents.

Trioxane (1), produced by cyclizing and trimerizing isobutylaldehydewith mineral acid, halogen, zinc chloride, phosphorous pentoxide and thelike, is a pure white crystal showing vapor pressures of 0.31 mmHg at20° C. and 0.95 mmHg at 30° C. with its melting point at 62.5° C.Another pure white crystal trioxane (2), also compounded by cyclizingand trimerizing trimethylacetaldehyde in the same method as above, showsvapor pressure of 0.12 mmHg at 20° C. and 0.38 mmHg at 30° C. and has amelting point of 92.0° C.

Both of the trioxanes are chemically stable, water-insoluble, andlighter inspecific gravity than water which enables them to float on thesurface of water, such property being advantageous for their adhesion topartially submerging plants such as paddy (rice) and the like. These twotrioxanes are tasteless and odorless and are able to maintain their formin the form of rough grain or pulverized powder even if they contain oilup to 20%, said property being advantageous for scattering. Thematerials are also moderately sublimable, which means they do notaccumulate within the soil. Sublimable agricultural compositions in theform of rough grains or pulverized powders produced by mixing eithertrioxane with one or more agricultural chemicals are such that theyattach to watery agricultural plants without undesirably scattering overa wide territory, wherein the compositions remain effective over a longperiod of time due to the moderate sublimability of the carriers. Thecompositions also produce the same effect when scattered on the soil.

the trioxanes of the present invention are nontoxic to men and domesticanimals and harmless to plants. We attempted to determine the LD_(50d)or median lethal dose of trioxane (1) by use of rats and mice, but theseattempts were in vain. Even as large a dose as 10,000 mg per kilogram ofbody weight caused no death. Also, trioxane (1) did not show eitherchronic or inhalation toxicity, nor did this material produce any toxicsubstances with activated sludges. This shows that said trioxane is verystable and is in no way toxic. Trioxane (2) presumably has similarproperties to trioxane (1) in this regard.

As described before, either trioxane (1) or (2) can be mixed with aninsecticide so as to volatilize the insect-killing vapor for a longperiod of time, which means that the product is desirable on acommercial scale for environmental sanitation, especially for domesticuse.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The following examples serve to illustrate the preferred method forpreparing the compositions of the present invention, the examplesimposing no limitation on the scope of claims in the present invention.(Hereinafter, "parts" denotes "weight parts".)

EXAMPLES

(Examples 1-16 cover insecticides, 17-20 fungicides, and 21-27herbicides.)

1. 970 parts of trioxane (1) was mixed evenly with 30 parts ofS-(1,2-dicarbethoxyethyl)-O,O-dimethyldithiophosphate (hereinaftercalled Malathion, to produce an insecticidal composition in the form ofrough powders for control of insects in a paddy field.

2. 980 parts of trioxane (1) was mixed thoroughly with 20 parts ofdimethyl-2,2-dichlorovinyl phosphate (hereinafter called DDVP) toproduce an insecticidal composition in the form of rough powders forcontrol of Musca domestica and insects on mulberry and tea trees.

3. 950 parts of trioxane (1) was mixed evenly with 50 parts ofO,O-diethyl-O-(2-isopropyl-4-methyl-pyrimidyl-(6))-thiophosphate(hereinafter called Diazinon to produce an insecticidal composition inthe form of rough powders for control of insects on paddy, fruit treesand vegetables.

4. 970 parts of trioxane (1) was mixed thoroughly with 30 parts ofO,O-dimethyl-O-(3-methyl-4-nitrophenyl)-thiophosphate to produce aninsecticidal composition in the form of rough powders for control ofinsects on paddy, fruit trees and vegetables.

5. 930 parts of trioxane (1) was mixed evenly with 70 parts ofethyl-O,O-dimethyldithiophosphorylphenylacetate to produce aninsecticidal composition in the form of rough powders for control ofinsects on paddy, fruit trees and vegetables.

6. 990 parts of trioxane (1) was mixed evenly with 10 parts ofO,O-dimethyl-1-hydroxy-2,2,2-trichloroethyl-phosphate to produce aninsecticidal composition in the form of rough powders for control of theflies, mosquitoes and cockroaches.

7. 950 parts of trioxane (1) was mixed evenly with 50 parts ofO,O-dimethyl-O-(3-methyl-4-methylthiophenyl) thiophosphate to produce aninsecticidal composition in the form of rough powders for control ofinsects on paddy, fruit trees and vegetables.

8. 930 parts of trioxane (1) was mixed evenly with 70 parts ofO,O-dimethyl-S-phthalimido-methyl dithiophosphate to produce aninsecticidal composition in the form of rough powders for control ofinsects on cotton.

9. 985 parts of trioxane (1) was mixed thoroughly with 15 parts ofethyl-O-p-nitrophenyl phenylphosphonothioate to produce an insecticidalcomposition in the form of rough powders for control of insects onpaddy, fruit trees and vegetables.

10. 980 parts of trioxane (2) was mixed evenly with 20 parts of2-sec.-butylphenyl-N-methylcarbamate to produce an insecticidalcomposition in the form of rough powders for control of insects onpaddy, fruit trees and vegetables.

11. 950 parts of trioxane (2) was mixed evenly with 50 parts ofl-naphthyl-N-methylcarbamate to produce an insecticidal composition inthe form of rough powders for control of insects on paddy, fruit treesand vegetables.

12. 990 parts of trioxane (2) was mixed evenly with 10 parts of2-isopropoxyphenyl-N-methylcarbamate to produce an insecticidalcomposition in the form of rough powders for control of insects onpaddy, fruit trees and vegetables.

13. 980 parts of trioxane (2) was mixed evenly with 20 parts of2-isopropylphenyl-N-methylcarbamate to produce an insecticidalcomposition in the form of rough powders for control of insects onpaddy, fruit trees and vegetables.

14. 980 parts of trioxane (2) was mixed evenly with 20 parts of3,4-xylyl-N-methylcarbamate to produce an insecticidal composition inthe form of rough powders for control of insects on paddy, fruit treesand vegetables.

15. 970 parts of trioxane (2) was mixed evenly with 30 parts ofm-totyl-N-methylcarbamate to produce an insecticidal composition in theform of rough powders for control of insects on paddy, fruit trees andvegetables.

16. 980 parts of trioxane (2) was mixed evenly with 20 parts of3,5-xylyl-N-methylcarbamate to produce an insecticidal composition inthe form of rough powders for control of insects on paddy, fruit treesand vegetables.

17. 830 parts of trioxane (1) was mixed evenly with 170 parts ofO,O-diisopropyl-S-benzylthiophosphate to produce a fungicidalcomposition in the form of pulverized powders for killing fungus onpaddy, etc.

18. 975 parts of trioxane (1) was mixed evenly with 25 parts ofO-ethyl-S,S-diphenyldithiophosphate (hereinafter called EDDP) to producea fungicidal composition in the form of pulverized powders for killingfungus on paddy, etc.

19. 970 parts of trioxane (2) was mixed evenly with 30 parts ofO-butyl-S-ethyl-S-benzyl-phosphorodithioate to produce a fungicidalcomposition in the form of pulverized powders for killing fungus onpaddy, etc.

20. 996.6 parts of trioxane (2) was mixed evenly with 3.4 parts of thehydrochloric salt of Kasugamycin to produce a fungicidal composition inthe form of pulverized powders for killing fungus on paddy, etc.

21. 910 parts of trioxane (1) was mixed evenly with 90 parts of2,4,6-trichlorophenyl-4'-nitrophenyl ether to produce a herbicidalcomposition in the form of pulverized powders for controlling weeds inpaddy fields.

22. 988 parts of trioxane (1) was mixed thoroughly with 12 parts ofallyl-2-methyl-4-chlorophenoxy acetate (hereinafter called MCP) toproduce a herbicidal composition in the form of pulverized powders forcontrolling weeds in paddy fields.

23. 915 parts of trioxane (2) was mixed thoroughly with 70 parts ofS-(4-chlorobenzyl)-N,N-diethyl-thiocarbamate and 15 parts of2-methylthio-4,6-(bis ethylamino)-1,3,5-triazine to produce a herbicidalcomposition for controlling weeds in paddy and plowed fields.

24. 915 parts of trioxane (1) was mixed thoroughly with 85 parts of3-amino-2,5-dichlorobenzoic acid to produce a herbicidal composition inthe form of pulverized powders for killing weeds in soybean fields.

25. 910 parts of trioxane (2) was mixed thoroughly with 90 parts of3-(3,4-dichlorophenyl)-1,1-dimethylurea to produce a herbicidalcomposition in the form of pulverized powder for killing weeds.

26. 915 parts of trioxane (2) was mixed thoroughly with 85 parts of3,4-dichloropropionanilide to produce a herbicidal composition in theform of pulverized powder for killing weeds in paddy fields.

27. 910 parts of trioxane (1) was mixed thoroughly with 90 parts ofS-(4-chlorobenzyl)-N,N-dimethyl-thiocarbamate to produce a herbicidalcomposition in the form of pulverized powder for killing weeds in paddyfields.

EXPERIMENTAL EXAMPLE 1

Paddy (Norin No. 8) was planted in three pots having a diameter of 12cm. One gram of the malathon composition prepared in Example 1 wassprinkled on the paddy in the first pot. One gram of powder containing97% of talc and 3% of Malathion was sprinkled on the paddy in the secondpot. No chemical was sprinkled on the one in the third pot for use as acontrol. On the day that the chemical was sprinkled, the fifth day andthe eighth day thereafter, 20 larvae of Nephotettix bipunctatuscincticeps were released in each pot and the number of killed larvae wascounted after 24 hours to determine the killing rate. The tests werecarried out in a thermostatic chamber and were repeated three times. Theresults of the tests are as follows:

    ______________________________________                                        When released                                                                            Killing Rate                                                       after      The same   Fifth day  Eighth day                                   sprinkling day        after      after                                        ______________________________________                                        Malathion +                                                                              100        90         63                                           trioxane (1)                                                                  Malathion +                                                                              100        61         5                                            talc                                                                          No chemical                                                                               0          0         0                                            (control)                                                                     ______________________________________                                    

These results show that the composition consisting of Malathion andtrioxane (1) remains effective for a longer period of time.

EXPERIMENTAL EXAMPLE 2

A mixture of trioxane (1), 30.0 grams, DDVP, 2.5 grams and Diazinon, 2.5grams, said three chemicals having been thoroughly mixed with eachother, were formed into a tablet measuring 60 mm in diameter and 12 mmin thickness. The single tablet was hung in a 1 m³ box at the centerthereof for determining the insect-killing effect of the tablet, putting20 Musca domestica in the box in a closed state on every test-conductingday, the testing results being shown in the table below:

    ______________________________________                                                                 Time required                                        Days of testing,                                                                           Weight      for entirely                                         starting with                                                                              of the      killing Musca                                        the setting of                                                                             tablet      domestica                                            the test-tablet                                                                            (Unit:g)    (Unit:minute)                                        ______________________________________                                         1st day     28.5        55                                                    3rd day     25.9        60                                                    5th day     24.3        60                                                   10th day     20.1        90                                                   20th day     12.5        180                                                  30th day      6.2        300                                                  ______________________________________                                    

EXPERIMENTAL EXAMPLE 3

A mixture of trioxane (2), 20 grams, DDVP, 3 grams and Diazinon, 1 gram,the three constituents having been mixed thoroughly with each other, wasformed into a tablet 60 mm in diameter and 8 mm thick. Said tablet wasput in to test a method quite identical with Example 24, except that thetesting period this time was longer by 10 days than in the case ofExperimental Example 3, the results being shown in the table below:

    ______________________________________                                                                 Time required                                        Days of testing                                                                            Weight      for entirely                                         starting with                                                                              of the      killing the                                          the setting of                                                                             tablet      Musca domestica                                      the test-tablet                                                                            (Unit:g)    (Unit:minute)                                        ______________________________________                                         1st day     22.0        11 60                                                 3rd day     20.1         60                                                   5th day     18.5         80                                                  10th day     15.1        100                                                  20th day     11.0        180                                                  30th day      7.5        330                                                  40th day      4.5        540                                                  ______________________________________                                    

EXPERIMENTAL EXAMPLE 4

Paddy (Norin No. 8) was planted in six pots having a diameter of 12 cm.After it has put forth tillers, 1 gram of the powdery EDDP compositionprepared in Example 18 was sprinkled on two pots. One gram of a powderycomposition consisting of 97.5% of talc and 2.5% of EDDP was sprinkledon the other two pots. No chemicals were sprinkled on the remaining twopots for use as control. The paddy in one of each pair of the pots wasinoculated on the day after sprinkling with Piricularia oryzae germs byspraying a suspension containing them. The paddy in the other of eachpair of the pots was similarly inoculated on the fifth day aftersprinkling. On the seventh day after inoculation, the area of thestill-infected portions was measured and indicated in terms ofpercentage against the infected area of the control paddy.

    ______________________________________                                                     Ratio to infected area of                                                     control paddy (in %)                                                          A          B                                                     ______________________________________                                        EDDP +         0             8                                                 trioxane (1)                                                                 EDDP + talc    0            47                                                No chemicals   100          100                                               used (control)                                                                ______________________________________                                         A: When inoculated on the day after sprinkling                                B: When inoculated on the fifth day after sprinkling                     

EXPERIMENTAL EXAMPLE 5

Four pots having a diameter of 10 cm were filled with soil of a paddyfield to the depth of 10 cm, on which 50 grains of seeds of barnyardgrass (Echinochloa crusgalli, Beauv., var. edulis, Honda) were sowed. Asmall amount of soil was put thereon and wetted with water. One gram ofpulverized powder of the MCP composition prepared in Example 22 wassprinkled on the first pot. On the second pot was sprinkled, one gram ofpowder consisting of 12 parts of MCP and 988 parts of diatomaceousearth. On the third pot was sprinkled one gram of trioxane (1) powderonly. No chemical was sprinkled on the fourth pot for use as a control.Twenty days later, the extent of germination of the grass in these fourpots was checked to determine the effect of herbicidal compositions.After the first check, 50 grains of the same seed were sowed on thefirst, second and third pots. In the case of the third pot, the grassthat had sprout was removed before re-sowing. Twenty days afterre-sowing, it was observed how much the germination was controlled. Theeffect of herbicidal compositions was evaluated against the control inthe fourth pot.

    ______________________________________                                               At first check                                                                             At second check                                                  (in %)       (in %)                                                    ______________________________________                                        1st pot   0              4                                                    2nd pot   0              78                                                   3rd pot  100            --                                                    4th pot  100            100                                                   ______________________________________                                    

The above experiments show that trioxane (1) has no herbicidal effect,does no harm to plants, and remains effective for a longer period oftime because of the small amount of decomposition of the herbicidecompared to the conventional MCP powder.

The amount of the carrier in respect to the active agriculturalingredients is not critical. The mixing ratio is essentially the same aswith conventional carrier-agricultural chemical combinations and dependson the type of material employed, the purpose of use, ease of use, thesafety requirements in respect to men and animals, etc.

A typical agricultural composition in accordance with the presentinvention contains about 80%-99.8% of a carrier.

What is claimed is:
 1. In a sublimable insecticidal composition in theform of rough grains, pulverized powders or tablets consistingessentially of an effective amount of at least one phosphate orcarbamate insecticide and a carrier therefor, said insecticide beingintimately mixed with the carrier, the improvement wherein the carrieris triisopropyl-s-trioxane having a melting point of 63.5° C. ortritertiarybutyl-s-trioxane having a melting point of 92.0° C.
 2. Acomposition according to claim 1 wherein the carrier istriisopropyl-s-trioxane.
 3. A composition according to claim 1 whereinthe carried is tritertiarybutyl-s-trioxane.
 4. A composition accordingto claim 1, wherein a single insecticide is employed.
 5. A compositionaccording to claim 1, wherein the insecticide isS-(1,2-dicarbethoxyethyl)-O,O-dimethyl-dithiophosphate.
 6. A compositionaccording to claim 1, wherein the insecticide isdimethyl-2,2-dichlorovinyl phosphate.
 7. A composition according toclaim 1, wherein the insecticide isO,O-diethyl-O-(2-isopropyl-4-methyl-pyrimidyl-(6))-thiophosphate.
 8. Acomposition according to claim 1, wherein the insecticide isO,O-dimethyl-O-(3-methyl-4-nitrophenyl)-thiophosphate.
 9. A compositionaccording to claim 1, wherein the insecticide isethyl-O,O-dimethyldithiosphosphoryl-phenylacetate.
 10. A compositionaccording to claim 1, wherein the insecticide isO,O-dimethyl-1-hydroxyl-2,2,2-trichloroethylphosphate.
 11. A compositionaccording to claim 1, wherein the insecticide isO,O-dimethyl-O-(3-methyl-4-methylthiophenyl) thiophosphate.
 12. Acomposition according to claim 1, wherein the insecticide isO,O-dimethyl-S-phthalimido-methyl dithiophosphate.
 13. A compositionaccording to claim 1, wherein the insecticide is ethyl-O-p-nitrophenylphenylphosphonothioate.
 14. A composition according to claim 1, whereinthe insecticide is 2-sec.-butylphenyl-N-methylcarbamate.
 15. Acomposition according to claim 1, wherein the insecticide is1-naphthyl-N-methylcarbamate.
 16. A composition according to claim 1,wherein the insecticide is 2-isopropoxyphenyl-N-methylcarbamate.
 17. Acomposition according to claim 1, wherein the insecticide is3,4-xylyl-N-methylcarbamate.
 18. A composition according to claim 1,wherein the insecticide is n-tolyl-N-methylcarbamate.
 19. A compositionaccording to claim 1, wherein the carrier is present in the compositionin an amount of 80-99.8%.
 20. A composition according to claim 4,wherein the carrier is present in the composition in an amount of80-99.8%.